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CN104130774A - Chlorosilicate fluorescent powder and preparation method thereof - Google Patents

Chlorosilicate fluorescent powder and preparation method thereof Download PDF

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CN104130774A
CN104130774A CN201410401127.4A CN201410401127A CN104130774A CN 104130774 A CN104130774 A CN 104130774A CN 201410401127 A CN201410401127 A CN 201410401127A CN 104130774 A CN104130774 A CN 104130774A
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carbonate
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CN104130774B (en
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鞠海东
王宝玲
马银海
陈世波
王海
吴琼
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Kunming University
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Kunming University
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Abstract

本发明公开了一种氯硅酸盐荧光粉，化学结构通式为LiM3-xSiO4Cl3:xR，M为Ca2+、Sr2+、Ba2+、Zn2+中的一种或几种，R为Ce、Eu、Tb、Pr中的一种或几种，0<x≤0.1。本发明所制得的荧光粉具有特定的晶体结构，可以通过调节M元素种类及含量来改变荧光粉的晶体结构，进而改变荧光粉的发射波长，该荧光粉可被300~460nm的光激发，并在可见光区域实现光的发射，有利于降低生产成本和制备不同色温和显色指数的白光LED。本发明还公开了上述荧光粉的制备方法，工艺简单，适合工业化。

The invention discloses a chlorosilicate fluorescent powder, the general chemical structure formula is LiM 3-x SiO 4 Cl 3 :xR, M is one of Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ or several, R is one or more of Ce, Eu, Tb, Pr, 0<x≤0.1. The phosphor powder prepared by the present invention has a specific crystal structure, and the crystal structure of the phosphor powder can be changed by adjusting the type and content of the M element, thereby changing the emission wavelength of the phosphor powder. The phosphor powder can be excited by 300-460nm light, And the emission of light is realized in the visible light region, which is beneficial to reduce the production cost and prepare white light LEDs with different color temperatures and color rendering indices. The invention also discloses a preparation method of the fluorescent powder, which has a simple process and is suitable for industrialization.

Description

A kind of Chlorosilicate phosphor powder and preparation method thereof
Technical field
The present invention relates to luminescent material technical field, be specifically related to fluorescent material, relate in particular to a kind of Chlorosilicate phosphor powder and preparation method thereof.
Background technology
In recent years, people more and more pay attention to energy-conservation and environmental protection, white light-emitting diode has that the life-span is long, volume is little, speed of response is fast, without mercury pollution and the advantage such as energy-efficient, application is in daily life more and more extensive, and preparation white color photodiode fluorescent material used also obtains flourish.Fluorescent material for white light-emitting diode mainly contains sulfide, nitride, molybdate and silicate etc. at present.Sulfide luminescent material is the main raw in red, green fluorescence powder, as (Ca 1- xsr x ) S:Eu 2+red fluorescence powder, Ga 2s 3: Eu 2+green emitting phosphor, but sulfide is unstable, at high temperature easily decomposes, and produces toxicant, and the white light LEDs life-span of preparation is short, and does not meet environmental requirement.People have developed again Sr 2si 5n 8: Eu 2+deng Nitride phosphor, these materials have good fluorescent characteristic, but in raw material, alkaline-earth nitride is easily and air and steam reaction, complicated process of preparation, and the powder purity making is low, at present can't scale operation.The excitation peak of molybdate fluorescent material is narrow, mates not good with LED chip; Glow color is single, mainly glows, and these have also limited its large-scale application.The luminescent material that the silicate of take is matrix has good chemical stability and thermostability, and high-purity silicon dioxide raw material inexpensive, be easy to get, maturing temperature is than features such as aluminates system are low, is more and more subject to people and payes attention to, and occurred Sr 2siO 4: Eu 2+, CaMgSi 2o 7: Eu 2+in fluorescent material, blue-light excited yellow fluorescent powder Sr wherein 3siO 5: Eu 2+luminous efficiency can compare favourably with YAG, and Lumi-tech company limited is for encapsulating white light LEDs, but the blue-light excited current efficiency of red, green silicate fluorescent powder is also lower, needs further improvement.
Recently, because muriate and silicate are all the efficient matrixes of supporting rare earth luminescence, by both compound Chlorosilicate phosphor powders have that synthesis temperature is low, stable chemical performance and luminosity advantages of higher, be subject to people's attention gradually.Yang Zhi equality people has reported rare-earth ion activated M 2siO 3cl 2the people such as (M=Ca, Sr, Ba), vast stretch of wooded country have reported rare-earth ion activated Ca 8mg (SiO 4) 4cl 2in fluorescent material, the synthesis temperature of these fluorescent material is reduced, at 850～1100 ℃.But these temperature are also higher from synthesis technique, the current matrix species of Chlorosilicate phosphor powder is also more rare in addition.Need to develop fluorescent material new, that synthesis temperature is lower, be conducive to reduce the preparation cost of fluorescent material.
Summary of the invention
The object of the present invention is to provide a kind of Chlorosilicate phosphor powder, this fluorescent material has good photoluminescent property, and can prepare at a lower temperature.
Another object of the present invention is to provide the preparation method of above-mentioned fluorescent material.
the object of the invention is to be achieved through the following technical solutions:
The chemical structure of general formula of luminescent material of the present invention is LiM 3-xsiO 4cl 3: xR, M is Ca 2+, Sr 2+, Ba 2+, Zn 2+in one or more, R is one or more in Ce, Eu, Tb, Pr, 0<x≤0.1.
Above-mentioned Chlorosilicate phosphor powder is to prepare by the following method:
1) raw material: adopt silicon oxide, Quilonum Retard and containing the carbonate of M element or oxymuriate as base starting material, adopt containing the oxide compound of R element or the raw material that muriate is incandescnet particle.
2) pre-treatment: according to LiM 3-xsiO 4cl 3: the stoichiometric ratio of xR takes respectively raw material, and raw material is ground to form to fine powder, and mixes;
3) roasting: the raw material mixing is positioned in corundum, graphite or boron nitride crucible, is rapidly heated and is heated to 600～900 ℃, and keep roasting in 2～10 hours at this temperature, slowly cool to subsequently room temperature;
4) aftertreatment: the powder after roasting is selected materials, grind, and with deionized water and the washing of small molecules organic alcohol solvent, remove residual foreign material, dry, obtain fluorescent material.
The above-mentioned carbonate containing M element is selected from one or more the combination in calcium carbonate, Strontium carbonate powder, barium carbonate or zinc carbonate.
The above-mentioned oxymuriate containing M element is selected from one or more the combination in calcium chloride, strontium chloride, bariumchloride or zinc chloride.
The above-mentioned oxide compound containing R element is selected from one or more the combination in cerium oxide, europium sesquioxide, terbium sesquioxide or Praseodymium trioxide.
The above-mentioned muriate containing R element is selected from one or more the combination in Cerium II Chloride, Europium trichloride, terbium chloride, praseodymium chloride.
The raw material that the preferred purity of above-mentioned raw materials is greater than 99%.
The kind of raw material is selected and the selection of amount, by those skilled in the art according to the present invention actual needs adjust voluntarily.
The above-mentioned preferred speed with 200～600 ℃/h that is rapidly heated heats up.
Above-mentioned roasting process carries out as good in the atmosphere of flowing air or hydrogen and nitrogen mixture.
Above-mentioned drying condition is preferably dried 2～10 hours at 60～200 ℃.
Above-mentioned roasting number of times is that whole process roasting number of times is at least once.
One or more mixing in above-mentioned small molecules organic alcohol solvent preferred alcohol, methyl alcohol, n-propyl alcohol.
Specifically, a kind of preparation method of above-mentioned fluorescent material, adopts following steps:
1) raw material: adopt silicon oxide, Quilonum Retard and containing the carbonate of M element or oxymuriate as base starting material, adopt containing the oxide compound of R element or the raw material that muriate is incandescnet particle;
2) pre-treatment: according to LiM 3-xsiO 4cl 3: the stoichiometric ratio of xR takes respectively raw material, and raw material is ground to form to fine powder, and mixes;
3) roasting: the raw material mixing is positioned in corundum, graphite or boron nitride crucible, with the speed of 300～600 ℃/h, be rapidly heated and be heated to 600～900 ℃, and at this temperature, keep roasting in 2～10 hours, slowly cool to subsequently room temperature, whole process is carried out in the atmosphere of flowing air or hydrogen and nitrogen mixture;
4) aftertreatment: the powder after roasting is selected materials, grind, and by deionized water and washing with alcohol, remove residual foreign material, dry at 60～200 ℃ 2～10 hours, obtain fluorescent material.
The described carbonate containing M element is selected from one or more the combination in calcium carbonate, Strontium carbonate powder, barium carbonate or zinc carbonate.
The described oxymuriate containing M element is selected from one or more the combination in calcium chloride, strontium chloride, bariumchloride or zinc chloride.
The described oxide compound containing R element is selected from one or more the combination in cerium oxide, europium sesquioxide, terbium sesquioxide or Praseodymium trioxide.
The described muriate containing R element is selected from one or more the combination in Cerium II Chloride, Europium trichloride, terbium chloride, praseodymium chloride.
Compared with prior art, the invention has the beneficial effects as follows:
1) the present invention is at LiEu 3siO 4cl 3on basis, built new substrate material LiM 3siO 4cl 3(M=Ca, Mg, Sr, Ba, Zn).
2) in raw material of the present invention, there are Quilonum Retard and alkaline earth metal chloride or zinc chloride, reduced the synthesis temperature of solid phase method, effectively reduce production cost.
3) fluorescent material that prepared by the present invention can be by the optical excitation of 300～460nm, and emission wavelength and luminous efficiency can regulate by controlling kind and the content of incandescnet particle, have higher chemical stability and thermostability.
4) preparation method of the present invention is simple, and synthesis temperature is lower, and the fluorescent material optical property making is good, therefore at White-light LED illumination or PDP demonstration field, has good application prospect.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
 
Fig. 1 is LiSr in embodiment 1 2.98siO 4cl 3: 0.02Eu 2+powder diffraction spectrum;
Fig. 2 is LiSr in embodiment 1 2.98siO 4cl 3: 0.02Eu 2+excite collection of illustrative plates;
Fig. 3 is LiSr in embodiment 1 2.98siO 4cl 3: 0.02Eu 2+transmitting collection of illustrative plates;
Fig. 4 is LiZn in embodiment 4 2.98siO 4cl 3: 0.02Tb 2+excite spectrogram;
Fig. 5 is LiZn in embodiment 4 2.98siO 4cl 3: 0.02Tb 2+transmitting spectrogram.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making all other embodiment that obtain under creative work prerequisite, belong to the scope of protection of the invention.
The embodiment of the present invention provides a kind of novel Chlorosilicate phosphor powder and preparation method thereof, thereby the synthesis temperature that can reduce current fluorescent material reaches the object reducing production costs.Below be elaborated.
Embodiment 1:
LiSr 2.98siO 4cl 3: 0.02Eu 2+synthesizing of fluorescent material.
According to stoichiometric ratio, taking purity is 0.0352 gram of europium sesquioxide that 2.21 grams of Strontium carbonate powders of 99.9%, 0.37 gram of Quilonum Retard, 0.61 gram of silicon oxide, 4.00 grams of Strontium dichloride hexahydrates and purity are 99.99%, the raw material taking is put in agate tank, adopts lapping mode by powder porphyrize and mix.
Subsequently the raw material mixing is positioned in corundum boat, in high temperature resistance furnace, at the gas mixture (N of nitrogen and hydrogen 2/ H 2=95:5) under atmosphere, in high temperature process furnances, with the temperature rise rates of 200 ℃/h, be heated to 750 ℃, and at this temperature, keep 2 hours, slowly cool to subsequently room temperature.
The powder grind into powder that sintering is obtained, removes residual foreign material by deionized water and washing with alcohol, dries 2 hours for 200 ℃, obtains the luminescenjt powder of even particle size.Adopting x-ray powder diffraction instrument to test fluorescent material, is target product according to the product of collection of illustrative plates 1 judgement preparation, adopts fluorescence spectrophotometer test fluorescent material to obtain collection of illustrative plates 2 and 3, and this fluorescent material can, by purple light and blue-light excited, be launched bright blue green light.
Embodiment 2:
LiCa 2.9siO 4cl 3: 0.1Eu 2+synthesizing of fluorescent material.
According to stoichiometric ratio, taking purity is 1.45 grams of calcium carbonate of 99.9%, 0.37 gram of Quilonum Retard, 0.61 gram of silicon oxide, 2.13 grams of 0.176 gram of europium sesquioxides that CALCIUM CHLORIDE DIHYDRATE purity is 99.99%, the raw material taking is put in agate tank, adopts lapping mode by powder porphyrize and mix.
Subsequently the raw material mixing is positioned in corundum boat, in high temperature resistance furnace, at the gas mixture (N of nitrogen and hydrogen 2/ H 2=95:5) under atmosphere, in high temperature process furnances, with the temperature rise rates of 600 ℃/h, be heated to 900 ℃, and at this temperature, keep 10 hours, slowly cool to subsequently room temperature.
The powder grind into powder that sintering is obtained, removes residual foreign material by deionized water and washing with alcohol, dries 10 hours for 60 ℃, obtains the luminescenjt powder of even particle size.
Embodiment 3:
LiBa 2.96siO 4cl 3: 0.02Eu 2+, 0.02Ce 3+synthesizing of fluorescent material.
According to stoichiometric ratio, taking purity is 2.92 grams of barium carbonates of 99.9%, 0.37 gram of Quilonum Retard, 0.61 gram of silicon oxide, 3.62 grams of 0.0352 gram of europium sesquioxide and 0.0344 gram of cerium oxide that barium chloride dihydrate purity is 99.99%, the raw material taking is put in agate tank, adopts lapping mode by powder porphyrize and mix.
Subsequently the raw material mixing is positioned in corundum boat, in high temperature resistance furnace, at the gas mixture (N of nitrogen and hydrogen 2/ H 2=95:5) under atmosphere, in high temperature process furnances, with the temperature rise rates of 300 ℃/h, be heated to 600 ℃, and at this temperature, keep 6 hours, slowly cool to subsequently room temperature.
The powder grind into powder that sintering is obtained, removes residual foreign material by deionized water and washing with alcohol, dries 7 hours for 100 ℃, obtains the luminescenjt powder of even particle size.
Embodiment 4
LiZn 2.98siO 4cl 3: 0.02Tb 3+synthesizing of fluorescent material.
According to stoichiometric ratio, taking purity is 1.21 grams of zinc oxide of 99.9%, 0.37 gram of Quilonum Retard, 0.61 gram of silicon oxide, 2.03 grams of zinc chloride, purity is 0.0366 gram of terbium sesquioxide of 99.99%, the raw material taking is put in agate tank, adopts lapping mode by powder porphyrize and mix.
Subsequently the raw material mixing is positioned in corundum boat, in high temperature resistance furnace, at the gas mixture (N of nitrogen and hydrogen 2/ H 2=95:5) under atmosphere, in high temperature process furnances, with the temperature rise rates of 600 ℃/h, be heated to 900 ℃, and at this temperature, keep 6 hours, slowly cool to subsequently room temperature.
The powder grind into powder that sintering is obtained, removes residual foreign material by deionized water and washing with alcohol, dries 3 hours for 60 ℃, obtains the luminescenjt powder of even particle size.
Adopt fluorescence spectrophotometer test fluorescent material to obtain collection of illustrative plates 4 and 5, this fluorescent material can, by purple light and blue-light excited, send bright green glow.
Embodiment 5:
LiCa 1.49sr 1.49siO 4cl 3: 0.02Eu 2+synthesizing of fluorescent material.
According to stoichiometric ratio, taking purity is 1.49 grams of barium carbonates of 99.9%, 0.37 gram of Quilonum Retard, 0.61 gram of silicon oxide, 4.00 grams of 0.0352 gram of europium sesquioxides that Strontium dichloride hexahydrate purity is 99.99%, the raw material taking is put in agate tank, adopts lapping mode by powder porphyrize and mix.
Subsequently the raw material mixing is positioned in corundum boat, in high temperature resistance furnace, at the gas mixture (N of nitrogen and hydrogen 2/ H 2=95:5) under atmosphere, in high temperature process furnances, with the temperature rise rates of 300 ℃/h, be heated to 800 ℃, and at this temperature, keep 4 hours, slowly cool to subsequently room temperature.
The powder grind into powder that sintering is obtained, removes residual foreign material by deionized water and washing with alcohol, dries 4 hours for 100 ℃, obtains the luminescenjt powder of even particle size.
Embodiment 6
LiCa 2.98siO 4cl 3: 0.02Pr 3+synthesizing of fluorescent material.
According to stoichiometric ratio, taking purity is 1.49 grams of calcium carbonate of 99.9%, 0.37 gram of Quilonum Retard, 0.61 gram of silicon oxide, 2.20 grams of 0.0330 gram of Praseodymium trioxides that CALCIUM CHLORIDE DIHYDRATE purity is 99.99%, the raw material taking is put in agate tank, adopts lapping mode by powder porphyrize and mix.
Subsequently the raw material mixing is positioned in corundum boat, in high temperature resistance furnace, under gas mixture (N2/H2=95:5) atmosphere of nitrogen and hydrogen, in high temperature process furnances, with the temperature rise rates of 600 ℃/h, be heated to 900 ℃, and at this temperature, keep 10 hours, slowly cool to subsequently room temperature.
The powder grind into powder that sintering is obtained, removes residual foreign material by deionized water and washing with alcohol, dries 10 hours for 60 ℃, obtains the luminescenjt powder of even particle size.
The fluorescent material that above embodiment obtains all can be by the optical excitation of 300～460nm, and luminous efficiency is high, and has higher chemical stability and thermostability.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof; , for one of ordinary skill in the art, according to thought of the present invention, all will change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention meanwhile.

Claims (8)

1.一种氯硅酸盐荧光粉，其特征在于，该材料的化学结构通式为LiM3-xSiO4Cl3: xR，M为Ca2+、Sr2+、Ba2+、Zn2+中的一种或几种混合，R为Ce、Eu、Tb、Pr中的一种或几种混合，0<x≤0.1。 1. A chlorosilicate fluorescent powder, characterized in that the general chemical structure of the material is LiM 3-x SiO 4 Cl 3 : xR, M is Ca 2+ , Sr 2+ , Ba 2+ , Zn 2 One or more mixtures of + , R is one or more mixtures of Ce, Eu, Tb, Pr, 0<x≤0.1. 2.如权利要求1所述荧光粉的制备方法，其特征在于：采用如下方法制备， 2. the preparation method of fluorescent powder as claimed in claim 1 is characterized in that: adopt following method to prepare, 1）原料：采用氧化硅、碳酸锂以及含M元素的碳酸盐或氯酸盐作为基质的原料，采用含R元素的氧化物或氯化物为发光粒子的原料； 1) Raw materials: Silicon oxide, lithium carbonate, and carbonate or chlorate containing M elements are used as raw materials for the matrix, and oxides or chlorides containing R elements are used as raw materials for luminescent particles; 2）预处理：按照LiM3-xSiO4Cl3: xR的化学计量比分别称取原料，将原料研磨成细小粉末，并混合均匀； 2) Pretreatment: Weigh the raw materials according to the stoichiometric ratio of LiM 3-x SiO 4 Cl 3 : xR, grind the raw materials into fine powder, and mix them evenly; 3）焙烧：将混合好的原料放置于刚玉、石墨或氮化硼坩埚内，快速升温加热到600～900℃，并在该温度下保持2～10小时焙烧，随后冷却至室温； 3) Roasting: Place the mixed raw materials in a corundum, graphite or boron nitride crucible, heat up rapidly to 600-900°C, and keep at this temperature for 2-10 hours for roasting, and then cool to room temperature; 4) 后处理：将焙烧后的粉体进行选料，研磨，并用去离子水和小分子有机醇溶剂洗涤，除去残留的杂物，烘干，获得荧光粉。 4) Post-processing: select the calcined powder, grind it, wash it with deionized water and a small molecule organic alcohol solvent, remove the remaining impurities, and dry it to obtain the phosphor. 3.如权利要求2所述的制备方法，其特征在于： 3. preparation method as claimed in claim 2 is characterized in that: 所述述含M元素的碳酸盐选自碳酸钙、碳酸锶、碳酸钡或碳酸锌中的一种或几种的组合； The carbonate containing M element is selected from one or more combinations of calcium carbonate, strontium carbonate, barium carbonate or zinc carbonate; 所述述含M元素的氯酸盐选自氯化钙、氯化锶、氯化钡或氯化锌中的一种或几种的组合； The chlorate containing M element is selected from one or more combinations of calcium chloride, strontium chloride, barium chloride or zinc chloride; 所述含R元素的氧化物选自氧化铈、氧化铕、氧化铽或氧化镨中的一种或几种的组合； The oxide containing the R element is selected from one or a combination of cerium oxide, europium oxide, terbium oxide or praseodymium oxide; 所述含R元素的氯化物选自氯化铈、氯化铕、氯化铽、氯化镨中的一种或几种的组合。 The chloride containing R element is selected from one or a combination of cerium chloride, europium chloride, terbium chloride and praseodymium chloride. 4.如权利要求2或3所述的制备方法，其特征在于： 4. the preparation method as claimed in claim 2 or 3 is characterized in that: 所述快速升温为以200～600℃/小时的速率升温。 The rapid temperature rise is a temperature rise at a rate of 200-600° C./hour. 5.如权利要求2或3所述的制备方法，其特征在于： 5. the preparation method as claimed in claim 2 or 3 is characterized in that: 所述焙烧过程可以在流动的空气或氢气与氮气混合气的气氛中进行。 The calcination process can be carried out in an atmosphere of flowing air or a mixed gas of hydrogen and nitrogen. 6.如权利要求2所述的制备方法，其特征在于：所述烘干条件在60～200℃下烘干2～10个小时。 6. The preparation method according to claim 2, characterized in that: the drying condition is 2-10 hours at 60-200°C. 7.如权利要求2或3或6所述的制备方法，其特征在于： 7. the preparation method as claimed in claim 2 or 3 or 6 is characterized in that: 所述小分子有机醇溶剂为乙醇、甲醇、正丙醇中的一种或几种混合。 The small molecule organic alcohol solvent is one or a combination of ethanol, methanol and n-propanol. 8.如权利要求1所述的荧光粉的制备方法，采用如下步骤： 8. The preparation method of fluorescent powder as claimed in claim 1, adopts the following steps: 1）原料：采用氧化硅、碳酸锂以及含M元素的碳酸盐或氯酸盐作为基质原料，采用含R元素的氧化物或氯化物为发光粒子的原料； 1) Raw materials: Silicon oxide, lithium carbonate, and carbonate or chlorate containing M elements are used as matrix materials, and oxides or chlorides containing R elements are used as raw materials for luminescent particles; 2）预处理：按照LiM3-xSiO4Cl3: xR的化学计量比分别称取原料，将原料研磨成细小粉末，并混合均匀； 2) Pretreatment: Weigh the raw materials according to the stoichiometric ratio of LiM 3-x SiO 4 Cl 3 : xR, grind the raw materials into fine powder, and mix them evenly; 3）制备：将混合好的原料放置于刚玉、石墨或氮化硼坩埚内，以２00～600℃/小时的速率快速升温加热到600～900℃，并在该温度下保持２～１０小时焙烧，随后缓慢冷却至室温，整个过程在流动的空气或氢气与氮气混合气的气氛中进行； 3) Preparation: Place the mixed raw materials in a corundum, graphite or boron nitride crucible, rapidly heat up to 600-900°C at a rate of 200-600°C/hour, and keep at this temperature for 2-10 hours for roasting , followed by slow cooling to room temperature, and the whole process is carried out in an atmosphere of flowing air or a mixture of hydrogen and nitrogen; 4) 后处理：将焙烧后的粉体进行选料，研磨，并用去离子水和乙醇洗涤，除去残留的杂物，在60～200℃下烘干2～10个小时，获得荧光粉； 4) Post-processing: select the calcined powder, grind it, wash it with deionized water and ethanol to remove residual impurities, and dry it at 60-200°C for 2-10 hours to obtain phosphor; 所述含M元素的碳酸盐选自碳酸钙、碳酸锶、碳酸钡或碳酸锌中的一种或几种的组合； The carbonate containing M element is selected from one or a combination of calcium carbonate, strontium carbonate, barium carbonate or zinc carbonate; 所述含M元素的氯酸盐选自氯化钙、氯化锶、氯化钡或氯化锌中的一种或几种的组合； The chlorate containing M element is selected from one or more combinations of calcium chloride, strontium chloride, barium chloride or zinc chloride; 所述含R元素的氧化物选自氧化铈、氧化铕、氧化铽或氧化镨中的一种或几种的组合； The oxide containing the R element is selected from one or a combination of cerium oxide, europium oxide, terbium oxide or praseodymium oxide; 　　所述含R元素的氯化物选自氯化铈、氯化铕、氯化铽、氯化镨中的一种或几种的组合。 The chloride containing R element is selected from one or a combination of cerium chloride, europium chloride, terbium chloride, and praseodymium chloride.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104736666A (en) * 2012-10-31 2015-06-24 海洋王照明科技股份有限公司 Silicate luminescent material and preparation method therefor
CN104736665A (en) * 2012-10-31 2015-06-24 海洋王照明科技股份有限公司 Silicate luminescent material and preparation method therefor
CN109111924A (en) * 2018-09-18 2019-01-01 江苏锐阳照明电器设备有限公司 A kind of LED light fluorescent powder and preparation method thereof that can improve yields
CN113717711A (en) * 2021-09-03 2021-11-30 昆明理工大学 Based on KCl to Pr3+Preparation method of X-ray induced photochromic material
CN116285962A (en) * 2023-02-27 2023-06-23 兰州大学 A kind of Eu2+ activated chlorine-containing silicate long afterglow material and its preparation method and application

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101307228A (en) * 2008-02-29 2008-11-19 中国计量学院 Chloroaluminosilicate fluorescent powder and preparation method thereof
CN101519591A (en) * 2009-04-08 2009-09-02 中国科学院长春光学精密机械与物理研究所 Green fluorescent powder for white light LED suitable for blue light excitation and preparation method thereof
CN101701155A (en) * 2009-10-26 2010-05-05 南昌大学 Chlorosilicate fluorescent powder and preparation method thereof
US20100156274A1 (en) * 2008-12-18 2010-06-24 Samsung Electronics Co., Ltd. Halosilicate phosphor and white light emitting device including the same
CN102660262A (en) * 2012-05-04 2012-09-12 苏州大学 A kind of Eu2+ activated calcium chlorosilicate fluorescent powder, preparation method and application
CN103343004A (en) * 2013-07-01 2013-10-09 彩虹集团公司 CaxSiO4Cly:Eu<2+> fluorescent powder and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101307228A (en) * 2008-02-29 2008-11-19 中国计量学院 Chloroaluminosilicate fluorescent powder and preparation method thereof
US20100156274A1 (en) * 2008-12-18 2010-06-24 Samsung Electronics Co., Ltd. Halosilicate phosphor and white light emitting device including the same
CN101519591A (en) * 2009-04-08 2009-09-02 中国科学院长春光学精密机械与物理研究所 Green fluorescent powder for white light LED suitable for blue light excitation and preparation method thereof
CN101701155A (en) * 2009-10-26 2010-05-05 南昌大学 Chlorosilicate fluorescent powder and preparation method thereof
CN102660262A (en) * 2012-05-04 2012-09-12 苏州大学 A kind of Eu2+ activated calcium chlorosilicate fluorescent powder, preparation method and application
CN103343004A (en) * 2013-07-01 2013-10-09 彩虹集团公司 CaxSiO4Cly:Eu<2+> fluorescent powder and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104736666A (en) * 2012-10-31 2015-06-24 海洋王照明科技股份有限公司 Silicate luminescent material and preparation method therefor
CN104736665A (en) * 2012-10-31 2015-06-24 海洋王照明科技股份有限公司 Silicate luminescent material and preparation method therefor
CN109111924A (en) * 2018-09-18 2019-01-01 江苏锐阳照明电器设备有限公司 A kind of LED light fluorescent powder and preparation method thereof that can improve yields
CN113717711A (en) * 2021-09-03 2021-11-30 昆明理工大学 Based on KCl to Pr3+Preparation method of X-ray induced photochromic material
CN113717711B (en) * 2021-09-03 2023-09-15 昆明理工大学 A method for preparing X-ray-induced photochromic materials based on KCl:Pr3+
CN116285962A (en) * 2023-02-27 2023-06-23 兰州大学 A kind of Eu2+ activated chlorine-containing silicate long afterglow material and its preparation method and application
CN116285962B (en) * 2023-02-27 2024-06-11 兰州大学 A Eu2+ activated chlorosilicate long afterglow material and its preparation method and application

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